An ultrafast surface-bound photo-active molecular motor.

We report the synthesis and surface attachment of an ultrafast light-driven rotary molecular motor. Transient absorption spectroscopy revealed that the half-life of the rate determining thermal step of the rotary cycle in solution is 38 ± 1 ns, the shortest yet observed, making this the fastest molecular motor reported. Incorporation of acetylene legs into the structure allowed the motors to be grafted to azide-modified quartz and silicon substrates using the "click" 1,3-dipolar cycloaddition reaction.

Driving unidirectional molecular rotary motors with visible light by intra- and intermolecular energy transfer from palladium porphyrin.

Driving molecular rotary motors using visible light (530-550 nm) instead of UV light was achieved using palladium tetraphenylporphyrin as a triplet sensitizer. Visible light driven rotation was confirmed by UV/vis absorption, circular dichroism and (1)H NMR spectroscopy and the rotation was confirmed to be unidirectional and with similar photostationary states, despite proceeding via a triplet instead of a singlet excited state of the molecular motor. Energy transfer proceeds in both inter- and intramolecular fashion from the triplet state of the porphyrin to the motor. Stern Volmer plots show that the rate of intermolecular quenching of the porphyrin excited state by the molecular motor is diffusion-controlled.

Reversing the direction in a light-driven rotary molecular motor.

Biological rotary motors can alter their mechanical function by changing the direction of rotary motion. Achieving a similar reversal of direction of rotation in artificial molecular motors presents a fundamental stereochemical challenge: how to change from clockwise to anticlockwise motion without compromising the autonomous unidirectional rotary behaviour of the system. A new molecular motor with multilevel control of rotary motion is reported here, in which the direction of light-powered rotation can be reversed by base-catalysed epimerization. The key steps are deprotonation and reprotonation of the photochemically generated less-stable isomers during the 360° unidirectional rotary cycle, with complete inversion of the configuration at the stereogenic centre. The ability to change directionality is an essential step towards mechanical molecular systems with adaptive functional behaviour.

Rotary molecular motors: a large increase in speed through a small change in design.

Reducing the steric interaction between the upper-half and the lower-half of a light-driven rotary molecular motor by decreasing the size of the aromatic moiety in the upper-half from a naphthalene to a benzothiophene results in an almost 3500 times faster rotation.

An enantioselective synthetic route toward second-generation light-driven rotary molecular motors.

Controlling the unidirectional rotary process of second-generation molecular motors demands access to these motors in their enantiomerically pure form. In this paper, we describe an enantioselective route to three new second-generation light-driven molecular motors. Their synthesis starts with the preparation of an optically active alpha-methoxy-substituted upper-half ketone involving an enzymatic resolution. The subsequent conversion of this ketone to the corresponding hydrazone by treatment with hydrazine led to full racemization. However, conversion to a TBDMS-protected hydrazone by treatment with bis-TBDMS hydrazine, prepared according to a new procedure, proceeds with nearly full retention of the stereochemical integrity. Oxidation of the TBDMS-protected hydrazone and subsequent coupling to a lower-half thioketone followed by recrystallization provided the molecular motors with >99% ee. As these are the first molecular motors that have a methoxy substituent at the stereogenic center, the photochemical and thermal isomerization steps involved in the rotary cycle of one of these new molecules were studied in detail with various spectroscopic techniques.

Light-driven altitudinal molecular motors on surfaces.

A Cu(I)-catalyzed 1,3-dipolar cycloaddition was used to construct a monolayer of an altitudinal molecular motor on quartz and silicon substrates, which represents the fastest light-driven molecular motor, to date, grafted to a solid surface.

A trimer of ultrafast nanomotors: synthesis, photochemistry and self-assembly on graphite.

Lightning quick! A new ultrafast light-driven molecular motor was developed, which was readily incorporated into a larger trimeric system. The trimer of these motors was studied with STM and at the interface of highly oriented pyrolytic graphite and 1-phenyloctane the molecules form stable arrays in which the chirality of the trimer is expressed on both the molecular and the supramolecular level (see figure).

Light-driven rotary molecular motors on gold nanoparticles.

We report the synthesis of unidirectional light-driven rotary molecular motors based on chiral overcrowded alkenes and their immobilisation on the surface of gold nanoparticles through two anchors. Using a combination of (1)H and (13)C NMR, UV/Vis and CD spectroscopy, we show that these motors preserve their photochemical and thermal behaviour after they have been attached to gold nanoparticles. Furthermore, we describe the synthesis of (2)H- and (13)C-labelled derivatives that were used to verify the unidirectionality of the rotary cycle of these motors both in solution and while grafted to gold nanoparticles. Taken together, these data support the conclusion that these motors maintain their unidirectional rotary cycle when grafted to the surface of small (ca. 2 nm) gold nanoparticles. Thus, continuous irradiation of the system under appropriate conditions leads to unidirectional rotation of the upper half of the molecules relative to the entire nanoparticle.

On the effect of donor and acceptor substituents on the behaviour of light-driven rotary molecular motors.

Light-driven rotary molecular motors based on overcrowded alkenes can be substituted with electron-donating and electron-withdrawing substituents (R = OMe, Cl and CN) in direct conjugation with the central double bond (the axis of rotation) without having a significant influence on the rate-limiting, thermal isomerisation step of their rotary cycle. This indicates that in this system, it is predominantly steric factors that determine the barrier to the thermal helix inversion. In contrast, the quantum yield and photoequilibria in the photochemical step were found to be quite sensitive to the combination of substituent and solvent employed.

A redesign of light-driven rotary molecular motors.

Structural modification of unidirectional light-driven rotary molecular motors in which the naphthalene moieties are exchanged for substituted phenyl moieties are reported. This redesign provides an additional tool to control the speed of the motors, and should enable the design and synthesis of more complex systems.

Rotational reorganization of doped cholesteric liquid crystalline films.

In this paper an unprecedented rotational reorganization of cholesteric liquid crystalline films is described. This rotational reorganization results from the conversion of a chiral molecular motor dopant to an isomer with a different helical twisting power, leading to a change in the cholesteric pitch. The direction of this reorganization is correlated to the sign of the change in helical twisting power of the dopant. The rotational reorganization of the liquid crystalline film was used to rotate microscopic objects 4 orders of magnitude larger than the bistable dopants in the film, which shows that molecular motors and switches can perform work. The surface of the doped cholesteric liquid crystalline films was found to possess a regular surface relief, whose periodicity coincides with typical cholesteric polygonal line textures. These surface features originate from the cholesteric superstructure in the liquid crystalline film, which in turn is the result of the presence of the chiral dopant. As such, the presence of the dopant is expressed in these distinct surface structures. A possible mechanism at the origin of the rotational reorganization of liquid crystalline films and the cholesteric surface relief is discussed.

Self-organized monolayer of meso-tetradodecylporphyrin coordinated to Au(111).

The structure of molecular monolayers formed at the interface between atomically flat surfaces and a solution of free-base meso-tetradodecylporphyrins (H2Ps) was examined by scanning tunneling microscopy (STM) at the liquid/solid interface. On the surface of graphite (HOPG), H2Ps form a well-ordered monolayer characterized by an oblique unit cell. On Au(111), H2Ps form a self-organized monolayer comprised of two distinct domain types. In both types of domains, the density of the porphyrin cores is increased in comparison to the arrangement observed on HOPG. Also, high-resolution STM images reveal that, in contrast to what is observed on HOPG, physisorption on Au(111) induces a distortion of the porphyrin macrocycle out of planarity. By using X-ray photoelectron spectroscopy, we demonstrate that this is likely to be due to the coordination of the lone pairs of the iminic (-C=N-) nitrogen atoms of the porphyrin macrocycle to Au(111).

Reversible three-state switching of luminescence: a new twist to electro- and photochromic behavior.

The fully reversible three-state blue/red/off emission from photo-/electrochromic substituted bis-thiaxanthylidenes is reported. The blue luminescence of the most stable (anti-folded) conformer of dimethyl- and dimethoxy-bis-thiaxanthylidene can be switched off by photochemical conversion to the meta-stable (syn-folded) conformer and switched on again by thermal reversion to the anti-folded state. The red luminescence of the bis-thiaxanthylium dication can be switched on by oxidation at approximately 1.0 and 1.2 V vs SCE of the syn- and anti-folded conformers respectively and switched off or to blue by reduction at approximately 0.35 V vs SCE.

Molecular machines: nanomotor rotates microscale objects.

Nanomachines of the future will require molecular-scale motors that can perform work and collectively induce controlled motion of much larger objects. We have designed a synthetic, light-driven molecular motor that is embedded in a liquid-crystal film and can rotate objects placed on the film that exceed the size of the motor molecule by a factor of 10,000. The changes in shape of the motor during the rotary steps cause a remarkable rotational reorganization of the liquid-crystal film and its surface relief, which ultimately causes the rotation of submillimetre-sized particles on the film.

Unidirectional molecular motor on a gold surface.

Molecules capable of mimicking the function of a wide range of mechanical devices have been fabricated, with motors that can induce mechanical movement attracting particular attention. Such molecular motors convert light or chemical energy into directional rotary or linear motion, and are usually prepared and operated in solution. But if they are to be used as nanomachines that can do useful work, it seems essential to construct systems that can function on a surface, like a recently reported linear artificial muscle. Surface-mounted rotors have been realized and limited directionality in their motion predicted. Here we demonstrate that a light-driven molecular motor capable of repetitive unidirectional rotation can be mounted on the surface of gold nanoparticles. The motor design uses a chiral helical alkene with an upper half that serves as a propeller and is connected through a carbon-carbon double bond (the rotation axis) to a lower half that serves as a stator. The stator carries two thiol-functionalized 'legs', which then bind the entire motor molecule to a gold surface. NMR spectroscopy reveals that two photo-induced cis-trans isomerizations of the central double bond, each followed by a thermal helix inversion to prevent reverse rotation, induce a full and unidirectional 360 degrees rotation of the propeller with respect to the surface-mounted lower half of the system.

A reversible, unidirectional molecular rotary motor driven by chemical energy.

With the long-term goal of producing nanometer-scale machines, we describe here the unidirectional rotary motion of a synthetic molecular structure fueled by chemical conversions. The basis of the rotation is the movement of a phenyl rotor relative to a naphthyl stator about a single bond axle. The sense of rotation is governed by the choice of chemical reagents that power the motor through four chemically distinct stations. Within the stations, the rotor is held in place by structural features that limit the extent of the rotor's Brownian motion relative to the stator.